Metallized monoazo reactive dyestuffs



United States Patent 3,207,745 METALHZED MUNQAZU REACTKVE DYESTUFFS PaulDussy, St. Louis, France, and Werner Bossard, Riehen, near Basel,Switzerland, assignors to J. R. Geigy A.G., Basel, Switzerland NoDrawing. Filed Mar. 16,1962, Ser. No. 180,318 Claims priority,application Switzerland, Mar. 17, M61, 3,234/61 6 Claims. (Ci. 260-146)The invention concerns reactive monoazo dyestuffs which are capable ofentering into a chemical linkage with cellulose. It also concernsprocesses for the production of these dyestuffs and their use to attainfast dyeings as well as the material fast dyed with the aid of thesedyestuffs.

It has now been found that valuable reactive monoazo dyestuffs areobtained if the diazo compound of an aromatic amine which can contain ametallisable group or a substituent which can be converted into such agroup in the o-position to the diazotisable amino group is coupled witha coupling component of the benzene, naphthalene or pyrazolone series,the components being so chosen that together they contain at least onepossibly further substituted arylureido radical and at least onesubstituent and if desired, metallisable dyestuffs are reacted with anagent giving off heavy metal of an atomic number of 24 to 29.

The new dyestuffs correspond to the general formula In this formula Eachof A and B independently is a benzene, naphthalene or pyrazoloneradical,

Aryl is a possibly substituted phenyl or naphthyl radical,

Of Y and Y one is oxygen and the other is oxygen or a carboxy, imino orimido group, but preferably oxy- Me is a heavy metal of an atomic numberof 24 to 29 possibly co-ordinated with uncoloured or coloured complexformers,

R is hydrogen or a possibly substituted low alkyl group,

Z is an organic radical which contains substituents which can be splitoff as anion groups capable of addition,

k, m and p are each a positive whole number of at most 2, and q is apositive whole number of at least 2.

Preferred dyestuffs according to the invention are obtained on usingsulphonated benzene and naphthalene diazo compounds and on usinghydroxynaphthalene and S-pyrazolone compounds as coupling componentsand, in addition, by so choosing the components that the end productcontains 2 to 6, preferably 3 to 4 sulphonic acid groups, only onepossibly substituted phenylureido group and only one amino groupsubstituted by a halogen dior tri-azinyl radical, in particular atrichloropyrimidylamino group. Me is preferably copper.

Dyestuffs according to the invention are also obtained by a modifiedprocess by using diazo and coupling components for the formation ofmonoazo dyestuffs by the ice process described above which, instead ofthe group contains a condensable amino group or a substituent which canbe converted into such a group, for example an acylamino group which caneasily be saponified or a nitro group. After the coupling is completeand, if necessary, acylamino groups have been saponified or nitro groupsreduced to amino groups, the condensable amino group is converted intothe group as defined by reaction with a compound introducing the radicalZ. Metallisable dyestuffs are reacted with an agent introducing heavymetal of the atomic numbers 24 to 29 in any suitable step in the abovechain of reactions, i.e. before or after the substituent has beenattained or reacted.

Dyestuffs according to the invention are also obtained by anothermodified process by using diazo and coupling components for theformation of monoazo dyestuffs by the process described above which,instead of the group -NH-CO-NH-aryl, contain a condensable amino group-NH or a substituent which can easily be converted into such, forexample an acylamino group which can be easily saponified or a nitrogroup. After completion of the coupling and, if necessary,saponification of acylamino groups or reduction of nitro groups to aminogroups, the amino group is converted into the group -NHCO-NH-aryl asdefined by reaction with a possibly further substituted arylisocyanateor aryl carbamic acid phenol ester. Again, metallisable dyestuffs arereacted with an agent introducing heavy metal of an atomic number of 24to 29 in any suitable step of the above series of reactions, i.e. beforeor after attainment or reaction of the substituent NH The radical (orthe radical to be converted thereinto) and also the possibly substitutedarylureido group (or the group to be converted thereinto) can be boundboth to the diazo component or to a radical thereof or to the couplingcomponent or a radical thereof and it can be bound direct to aromaticrings thereof or in an external position to substituents of the latter.It can also be bound to the aryl radicals of benzoylamino groups.

In the radical in addition to hydrogen, R is, for example, methyl,ethyl, propyl, butyl, hydroxyethyl, hydroxypropyl, cyanoethyl, benzyl; Zis the radical making the chemical linkage with the cellulose fibrepossible. This radical contains, as mobile substituents which can besplit off as anions, in a suitable position, principally halogen suchas, particularly chlorine or bromine, or sulphated alcoholic hy droxylgroups O-SO H or salts thereof with alkalies, or as grouping capable ofaddition, e.g., an olefinic group adjacent to an electrophilic group. Zis, for example, an aliphatic acyl radical having halogen in the[3-position, e.g. the fi-chloroor, particularly, fi-bromopropionylradical, or an aliphatic unsaturated acyl radical, e.g., the acroylradical, crotyl radical, maleoyl radical or fumaroyl radical, the 06- orfi-chloio, 06- or fi-bromoacroyl radical or 06-- or ,B-crotoyl radical,the chlorofumaroyl radical, in addition a sulphated fl-hydroxyethyl orfl-hydroxypropyl radical, if R is hydrogen. However, Z is principally ahalogenazinyl radical which contains one or two groupings Hal as ringcomponents, wherein Hal is principally chlorine, or also bromine. Inthis case, Z is, e.g. a dichloroor dibromopyrimidyl radical, adichlorobromopyrimidyl radical, a dichloro-1,3,5-triazinyl radical or amonochchloroor monobromo-l,3,5tryazinyl radical which contains asfurther substituents, e.g. phenyl, alkoxy, alkylrnercapto groups oramino groups and, in particular, substituted amino groups such as, e.g.,sulphonated phenylamino groups.

Agents introducing the radical Z into condensable groups are the acidhalides, in particular the acid chlorides or also the acid bromides oracid anhydrides of carboxylic acids which contain in the acid radicalthe reactive substituents or groups capable of addition given above.However these are, in particular, cyclic imide halides of carbonic acidin which the reactive grouping Hal occurs more than once as component ofa six-membered heterocyclic ring such as, e.g. cyanuric chloride, 2,4,6-trichloroor 2,4,6-tribromopyrimidine, 2,4,5,6-tetrachloropyrimidine,2,4,6-trichloro-5-bromopyrimidine, 2,4-dichloro-6-alkoxy-,-6-alkylthio-, -6-phenyl-, sul hophenylamino- 1,3,5-triazine etc. Careis taken by suitable choice of reaction conditions that only one of themobile halogen atoms reacts and that it reacts with the condensablegroup Depending on the reactivity of the components, the reaction isperformed at temperatures as low as possible, e.g., 0 to 60 C., at pHvalues of the aqueous solution of 4 to at most 9, and in the presence ofbutler salts such as alkali metal salts of polyvalent inorganic acids orof organic acids as mineral acid binding agents, e.g., using the sodiumsalts of phosphoric acids, carbonic acid, acetic acid. Naturally, theconditions for the reac tion of the group in the dyestuif structure alsopertain for the production of diazo and coupling compounds usableaccording to the invention from intermediate products which contain acondensable group As already mentioned, the arylureido group can beunsubstituted or substituted, in the latter case it can contain, e.g.inert substituents such as halogen, alkyl, alkoxy, alkylsulphonyl orsulphamyl groups possibly substituted at the nitrogen atom. Inparticular, it can also contain salt-forming substituents such as thesulphonic acid group or condensable or substituted amino groups, e.g.,acylated or halogenazinylated amino groups, or amino groups. Diazocomponents having an arylureido group according to the invention areobtained, for example, by reacting an aromatic bisprimary amino compoundhaving a sterically hindered amino group with an aryl isocyanate or withan arylcarbamic acid phenol ester the aryl radical of which can also besubstituted. Examples of such bis-primary amino compounds with asterically hindered amino group are 1,3-diaminobenzenet-sulphonic acidand l,4-diaminobenzene-Z-sulphonic acid as well as their mono-mormono-paminobenzoyl derivatives. For the same purpose, also aromaticprimary monoamines, in particular aminobenzene or aminonaphthalenesulphonic acids not having a sterically hindered amino group, can bereacted with nitroaryl iscyanates and the nitro group reduced to theamino group. Coupling components containing arylureido groups areobtained from azo components having a condensable primary amino groupwhich does not or does not alone ailect the coupling power, and from theaminobenzoyl derivatives thereof by reaction with aryl isocyanates orphenylcarbamic acid phenol esters. Suitable starting materials are, inparticular, aminonophthalene sulphonic acids and their mandpaminobenzoyl derivatives.

Examples of diazo components containing an arylureido group which areusable according to the invention are: 4-amino-diphenylurea-3,3'-disulphonic acid, 3-aminodiphenyl urea-4,3'disulphonic acid,4-amino-diphenyl urea-3,4'-disulphonic acid, 3-amino-diphenyl urea-4,4-disulphonic acid, 4-amino-4-hydroxy-diphenyl urea-3- carboxylicacid-3,5-disulphonic acid, 3-amino-4'-hydroxydiphenyl urea-3'-carboxylicacid-4,5-disulphonic acid, 3- aminophenyl-naphthyl- 2-urea-4,4,8-trisulphonic acid, 4-amino-phenyhnaphthyh(2)-urea 3,4',8'trisulphonic acid, 4-amino phenyl naphthyl-(1)-urea-3,3,6-trisulphonicacid, 3-amino-phenyl-naphthyl-(1')-urea-4,3',6- trisulphonic acid.

Examples of diazo compounds usable according to the invention whichcontains a radical are:1-arnino-3-[3,5',6'-trichloropyrimidyl-(4)-amino]- benzene-G-sulphonicacid, l-amino-4-[2,5',6'-trichloropyrimidyl-(4)-amino]- benzene,sulphonic acid, 1-amino-3-[2,6-dichloropyrimiclyl-(4')-amino]-benzene-6-sulphonic acid, 1-amino-4- [2',6-dichloropyrimidyl- (4'-amino]- benzene-Z-sulphonic acid,1-amino-3-[5-bromo-2',6'-dichloropyrimidyl-(4)- amino]-benzene-6-sulphonic acid, l-amino-3-[4,6'-dichlorotriazinyl-(2)-amino]-benZene-6-sulphonic acid, 1-a1nino-4-[4,6'-dichlorotriazinyl-(2')amino]-benzene-Z-sulphonic acid,l-amino-3-[4,(3"-sulphophenylamino)-6'-chlorotriazinyl-(2')-amino]-benzene-6-sulphonicacid l-amino-3-[4-methoxy-6-chlorotriazinyl (2)-amino]- benzene6-.sulphonic acid,

1-an1ino-4[4'-methoxy-6'-chlorotriazinyl-(2')-amino] benzene 2-sulphonicacid,

1-amino-3 [4-amino-6'-chlorotriazinyl- 2') -amino benzene-6-sulphonicacid,

1-amino-4-(B-chloropropionyl-amino)-benzene-2- sulphonic acid,

1-arnino-3-( Q-chlorocrotonyl-amino)benzene-6- sulphonic acid,

1-amino-3-(acryloamino)-benzene-6-sulphonic acid,

1-amino-3-[2',5,6-trichloropyrimidyl-(4)-methy1-amino]-benzene-6-sulphonic acid,

1-amino-3- [4',6-dichlorotriazinyl- 2' -methyl-amin] benzene-6-sulphonicacid,

1-amino-3- [4-dimethylamino-6'-chlorotriazinyl- 2'amino]-benzene-6-sulphonic acid.

As examples of diazo compounds usable according to the invention whichcontain a group capable of forming the metal complex or a substituentwhich is easily converted into a metallisable group under themetallising conditions, are mentioned:

1-arnino-2-methoxybenzene-S-sulphonic acid, l-amino-Z-methoxybenzene-4-sulphonic acid, l-amino-Z-hydroxybenzene-S-sulphonicacid, 1-amino-2-hydroXybenzene-3,5- disulphonic acid,l-amino-2-hydroxybenzene-S-methylsulphone,1-amino-2-hydr0xybenzene-S-ethylsulphone, lamino-2-hydroxynaphthalene-4-or -6- sulphonic acid, 1-amino-2-hydroxynaphthalene-4,G-disulphonicacid, 2- amino-l-hydroxynaphthalene4-sulphonic acid.

The last mentioned diazo components are used advantageously for thecoupling with an azo component coupling in a position adjacent to aphenolic, naphtholic or enolic hydroxyl group whilst observing theconditions pertaining to choice as defined and the dyestuffs obtainedare metallised advantageously by reacting with agents giving olf copperin any suitable step of the reaction sequence.

Other diazo components which can be employed for coupling with azocomponents which contain the arylureido and groups as defined are:

1-arninobenzene-Z-sulphonic acid, l-arninobenzene-2,4- or2,5-disulphonic acid, 1-amino-4-methylor -methoxyor-ethoxybenzene-Z-sulphonic acid, 1-amino-5-aoetylaminoor -benzoylaminobenzene-Z-sulphonic acid, 2- aminonaphthalene-l-sulphonic acid,Z-aminonaphthalene- 1,5-disulphonic acid.

Examples of azo components Which contain both an arylureido group andthe radical Which are to be coupled with the diazo components mentionedin the previous paragraph and others similar thereto are:

Condensation product from one equivalent of 2,4,5,6-tetrachloropyrimidine, -bromo-2,4,6-trichloropyrimidine,2,4,fi-trichloropyrimidine, cyan-uric chloride, 2-amino-4,6-dichlorotriazine, Z-ethoxyor Z-methoxy- 4,6dichlorotriazine, 2-(2-, 3'-or 4'-sulphophenylamino)-4,6-dichlorotriazine, ,B-chloroorfi-bromopropionyl chloride, acrylic chloride, B-chloroor fl-bromoacrylicchloride and an equivalent of l-(3'- or 4-aminophenylureido)-5-hydroxynaphthalene-7-sulphonic acid, 2-(3'- or 4-aminophenylureido)-5-hydroxynaphthalene 7 sulphonic acid, 2-(3- or4'-aminophenylureido)-6-hydroxynaphthalene-8-sulphonic acid, 2-('3- or4'-arninophenylureido)-8-hydroxynaphthalene-6-sulphonic acid, 1-(3' or4'-aminophenylureido)-8-hydroxynaphthalene-3,5- or 3,6- or4,6-disulphonic acid.

Examples of coupling components containing an arylureido group which canbe used according to the invention are:

1-(3'- or 4'-sulphophenylureido)-5hydroxynaphthal ene-7-sulphonic acid,2-(3'- or 4'- sulphophenylureido)- S-hydroxynaphthalene-7-sulphonicacid, 2-(3- or 4'- sulphophenylureido) 8 hydroxynaphthalene 6 sulphonicacid, 2-(3- or 4- sulphophenylureido)-6-hydroxynaphthalene-S-sulphonicacid, 1- or 2- (4-hydroxy-3-carboxy- 5-sulphophenylureido) 5hydroxynaphthalene-7-sulphonic acid,2-(4'-hydroxy-3'-carboxy-5-sulphopheny1ureido)-8-hydroxynaphthalene-6-sulphonic acid, 2-(4'- hydroxy-3'-carboxy5' sulphophenylureido)-6-hydroxynaphthalene-8-sulphonic acid, 1-(3,6'-or 4,6- or 4,7- disulphonaphthyl-(1)-ureido) 5 hydroXynaphtha1ene-7-sulphonic acid, 2-(3',6- or 4,6'- or 4,7-disulphon aphthy1-( l )-ureido-S-hydroxynaphthalene-7-sulphonic acid, 2-(4',8- or 5,7- or6,8'-disulphonaphthyl-(2)-ureido)- S-hydroxynaphthalene-7-su1phonicacid, 2-phenylureido- 8-hydroxynaphthalene-6-su1phonic acid,2-phenylureido- -hydroxynaphthalene-B-sulphonic acid, 1- or2-phenylureido-5-hydroxynaphthalene-7-sulphonic acid,l-phenylureido-8-hydroXynaphthalene-3,5- or -3,6- or -4,6- disulphonicacid.

Examples of coupling components containing a radical which can be usedaccording to the invention are:

1[2',5,6 trichloropyrimidyl-(4')-amino]5-hydroxynaphthalene 7 sulphonicacid, 2-[2',5,6'-trich1oropyrimidyl (4)amino]-5-hydroxynaphthalene-7-sulphonic acid, 2-2',5',6-trichloropyrimidyl- (4' arnino] 6-hydroxynaphthalene-8-sulphonicacid, 2-[2',S,6'-trichloropyrimidyl (4') amino]-8-hydroxynaphthalene-6-sulphonic acid, 2-[2,6'-dichloropyrimidyl-(4')-arnino]-S-hydroxynaphthalene-7-sulphonic acid,2-[2',6'-dich1oropyrimidyl-(4')-arnino] 8 hydroxynaphthalene 6 sulphonicacid, 2-[5-bromo2',6-dichloropyrimidyl-(4)-amino]-5-hydroxynaphthalene-7-sulphonic acid, 2-[4',6'-dichlorotriazinyl (2) amino]-5-hydroxynaphthalene- 7-sulphonic acid, 2-[4',6'-dichlorotriazinyl-(2')-amino]- 8-hydroxynaphthalene-6-sulphonicacid, 2-[4'-methoXy-6' chlorotriazinyl (2) amino]-5-hydroxynaphthalene-7sulphonic acid, 2-[4'-amino-6-chlorotriazinyl (2')-amino]-5-hydroxynaphthaleneJ-sulphonic acid, 2-[4- (4"sulphophenylamino)-6'-chlorotriazinyl-(2')-amino]-S-hydroxynaphthaleue-7-sulphonic acid, 2-[4'-(3"-sulphophenylamino-6-chlorotriazinyl--(2') amino] -8-hydroXynaphthalene-6-sulphonic acid,1- or Z-(fi-chlo-ropropionylamino)-, 1- or Z-(fi-chloroacrylamino)-, lor2-(5- chlorocrotonylamino)-, 1- or Z-(B-bromocrotonylamino)-, 1- or2-crotonylamino-, 1- or 2-maleonylarnino-, or 1- or 2-acrylamino-S-hydroxynaphthalene-7-sulphonic acid, 1-[2.,5',6-trichloropyrimidyl(4') amino]-8 hydroxynaphthalene-3,6-, -3,5- or -4,6- disulphonic acid,1-[5' bromo'2,6-dichloropyrimidyl (4) amino]-8-hydroxynaphthalene-3,6-,-3,5- or -4,6-disulphonic acid, 1-[2',6 dichloropyrimidyl-(4')-amino] 8hydroxynaphthalene- 3,6-, -3,5- or 4,6- disulphonic acid,l-[4',6'-dich1orotriazinyl-(2)-amino]-8-hydroxynaphthalene-3,6-, -3,5-or -4,6-disulphonic acid, 1'-[4'-ethoxy-6'-chlorotriazinyl-(2')-arnino]-8-hydroxynaphthalene-3,6-, ,-3,5- or -4,6- disulphonicacid, 1-[4'-amino-6-chlorotriazinyl-(2')-amino]-8-hydroxynaphthalene-3,6-, -3,5- or -4,6- disulphonic acid,1-[4'-(3-sulphophenylamino)-6-chlorotriaziuyl-(Z')-amino]-8hydroxynaphthalene-3,6-,-3,5- or -4,6- disulphonic acid, 1-(fl chloropropionylamino)-, 1-(fi-chloroacrylamino)-, 1 (,8 bromocrotonylamino}, cr-otonylan1ino-,maleonylarninoor acroylamino-8-hydroXynaphthalene-3,6-, -3,5- or -4,6-disulphonic acid, 1- or 2-[2,5',6-trichloropyrimidyl-(4)-rnethylamino]-5- hydroxynaphthalene-7-sulphonic acid, 2-[2',5'6'-trichloropyrimidyl-(4)-methylamino] 8 hydroxynaphthalene-6-sulphonicacid, 2-[4-ethoxy-6-chlorotriazinyl-(2)-ethylamino]-5-hydroxynapththalene 7 sulphonic acid,2-[4'-(3-sulphophenylamino) 6' chlorotriazinyl-(2')methylamino]-8-hydroxynaphthalene 6 sulphonic acid.

Examples of other coupling components which are coupled with diazocomponent containing the defined arylureido and groups are:

"1-hydroxynaphthalene-3,6-, -3,8-, -4-,6-, -4,7- or -4,8- disulphonicacid, Z-hydroxynaphthalene-3,6-, -3,7-, -4,8-, -5,7 or -6,8- disulphonicacid, l-hydroxynaphthalene- 3,6,8-trisulphonic acid,2-hydroxynaphthalene-3,6,8-trisulphonic acid,1-benzoylamino-8-hydroxynaphthalene- 3,6-, -3,5- or -4,6- disulphonicacid, l-amino-S-hydroxynaphthalene-2,4-disulphonic acid, 1 amino 8hydroxynaphthalene-Z-sulphonic acid,Z-amino-S-hydroxynaphthalene-lfl-disulphomc acid,Z-amino-8-hydroxynaphthalene-3,6-disulphonic acid.

Examples of diazo components containing both an arylnreido group and agroup to be coupled therewith are:

Condensation product from one equivalent of 2,4,5,6-tetrachloropyrimidine, bromo 2,4,6-trichloropyrimidine,2,4,6-trichloropyrimidine, cyanuric chloride, 2- amino4,6-dichlorotriazine, Z-ethoxyor 2-methoxy- 4,6- trichlorotriazine,2(2'-, or 3'- or 4'- sulphophenylamino) 4,6-dichlorotriazine, Bchloropropionyl chloride, ,B-bromopropionyl chloride, acrylic chloride,p-chl-oroacrylic chloride or ,B-bromoacrylic chloride and one equivalentof 3,3'-diaminodiphenyl urea-4-sulphonic acid, 3,4-diaminodiphenylurea-4-sulphonic acid, 4,3'-diaminodiphenyl urea-3-sulphonic acid,4,4'-diaminodiphenyl nrea-3-sulphonic acid.

The diazo components are diazotised with nitrous acid or the alkalimetal salts thereof in the usual way in a mineral acid medium at lowtemperatures.

In order to avoid t=oo previous reaction of reactive substituents, mildconditions are indicated both in the coupling as well as in theisolation and drying of the dyestuffs. Advantageously aqueous phaseshaving low pH values of at most 8 are used and, after completion of thecoupling, if necessary the pH is lowered to 4-6 by the addition of acidfor the isolation and drying.

The dyestuffs are dried advantageously as quickly as possible at not toohigh temperatures, in particular under reduced pressure. Further detailsas to method can be 'seen from the following examples.

Particularly valuable reactive dyestulfs correspond to the formulawherein E and E are independent radicals of the benzene, naphthalene orpyrazolone series. Monoazodyes of the benZene-azonaphthole series arepreferred.

The radical D is preferably an unsubstituted phenyl radical. D can alsobe a substituted phenyl radical, particularly when n is 0, assubstituents are preferred sulfonic acid, carboxylic acid and hydroxygroups.

The radical R is hydrogen or a lower alkyl, as lower alkyl especiallyalkyl having one or two carbon atoms, the methyl group being preferred.

One of Y and Y is O and the other of Y and Y is preferably -O, but itcan also be CO",

Me is in particular copper, but it can also be chromium or cobalt, ifdesired the chromium or cobalt is co-ordinated with uncoloured andcoloured complex formers.

One of n and n is the number 0 and the other of n and n is the number 1.

q represents a low whole number of 3 to 5 inclusive, preferably thenumbers 3 or 4, and

k is preferably the number 1, but it can also be 2.

The SO H moieties in the above formula are conventionally on one or moreof the aromatic nuclei.

If E and E is a radical of the benzene series it is preferably theunsubstituted phenyl, but it can also be substituted, e.g. with nitro orwith a carboxylic acid group. If E or E is a radical of the naphthaleneseries it is eg. the unsubstituted naphthyl or preferably thehydroxynaphthyl, which if desired can be substituted by a benzoylaminogroup. If at least one of E and E is a radical of the pyrazolone series,it is preferably a lphenylor a l-naphthyl-S-methyl-S-pyrazolone radical.

Examples of the reactive radical Z are principally:

(a) Polyhalogen-pyrimidyl radicals such as dihalogen pyrimidyl radicals,e.g. the 2,6-dichloro-pyrimidyl-(4) or the 2,6-dibromopyrimidyl-(4)-radical which can contain a substituent in the remaining position, inparticular a further halogen atom, e.g. the 2,5,6-trichloropyrimidyl-(4) radical or the 2,6-dichloro-5-bromo-pyrimidyl-(4) radical.

(b) Halogen-1,3,5-triazinyl radicals which in the remaining positioncontain a substituent, in particular halogen, primary amino, arylaminoor alkoxy groups, e.g. the 4,6-dichloro- 1,3,5-triazinyl radical, the 4chloro-6- amino or 4-chloro-6asulphophenylamino- 1,3,5-triazinylradical, the 4-chloro-6-methoxyor 4-chlor0-6-eth0xy- 1,3,5-triazinylradical.

(0) Lower fi-halogen fatty acid radicals containing at most 4 carbonatoms such as p-halogen alkanoyl radicals, e.g. the ,B-chloropropionylradical and particularly ,8- halogen alkenoyl radicals, e.g. the,B-chloro-acrylyl radical, the ,B-chlorocrotonyl radical.

Halogen in the radicals mentioned is, in particular, chlorine but it canalso be bromine.

(d) Groups capable of addition such as In addition, dyestuffs whichcontain the dichloropyrimidyl group and, especially, thetrich-loropyrimidyl group are preferred.

The new dyestuffs are yellow, orange, red, violet, blue, brown to blackpowders which, in the form of their alkali metal salts dissolve well inwater. They are suit able for the dyeing and printing of fibres, inparticular natural or regenerated cellulose fibres and natural orsynthetic polyarnide fibres, in yellow, orange, red, brown and violet,blue, grey to black shades. The cellulose material is impregnated orprinted advantageously at a low temperature, e.g. at 2050 C., with thepossibly thickened dyestutf solution and then the dyestuif is fixed bytreatment with acid binding agents. Examples of such are sodiumcarbonate, potassium carbonate, diand tri-sodiurn phosphate, causticsoda lye and, at temperatures of over 50, also potassium or sodiumcarbonate. The treatment with these agents can be performed at roomtemperature or at a raised temperature. Instead of subjecting theimpregnated materials to an alkaline after-treatment, the acid bindingagent can, in many cases, also be added to the impregnating liquors orprint ing pastes, after which the dyeing is developed by a short heatingto temperatures of over to or by storing for a longer time at roomtemperature.

The new dyestuffs are chemically bound to the fibre by the treatmentwith acid binding agents and, after soaping to remove non-fixeddyestuffs, the cellulose dyeings in particular have excellent wetfastness properties. Compared with analogous dyestuifs which do notcontain the arylureido group as defined, the dyestuffs according to theinvention have, as a particular advantage, an increased substantivity tocellulose. They are suitable, therefore, for

water. 24.0 parts of finely pulverized tetrachloropyri-midine are thensprinkled in within 1 hour, care being taken that, by the simultaneousaddition dropwise of sodium carbonate solution, the reaction mixturealways remains neutral. As soon as no more free amino groups can beB-anainodiphenyl urca-4,3-disulphonie acid o 4-aminodipheny1urea-3,4-disulphonie acid suphonic acid.

2 (3aminophenylurcido)-8-hydroxynaphthalcne-G- sulphonic acid.

l-(4-arninophenylureido) -8-hydroxynaphthalene-3,6-

the dyemg of cellulose from a bath having a low ratio of traced, the newdyestuff 1S preclp tated with sodium chlogoods to liquor in particularin the presence of salts ride solution, filtered off, washed with dilutesodium chlo- Which accelerate the drawing of the dyestuif such as ridesolution and dried in vacuo at 60. It is a dark red G-laubers salt orsodium chloride. It is surprising that, powder which dissolves in waterwith an orange-red in spite of this increased substantivity, non-fixeddyestuff 10 colour. can be very easily and completely washed out whichis 4 parts of the new dyestuif are dissolved in 1000 parts one of themost important conditions for good wet of water and 20 parts of sodiumcarbonate are added. fastness properties of cellulose dyeings attainedwith re- 100 parts of cotton are entered at 40, the bath is heatedactive dyestufis. to 90-95 within 30 minutes, 80 parts of sodiumchloride The following examples illustrate the invention. Where areadded and dyeing is performed for 1 hour at this not otherwise expresslystated, parts are given therein temperature. The goods are then rinsedand soapcd at as parts by weight. The temperatures are in degrees theboil for 15 minutes. A deep, brilliant orange dyeing .centigrade. Therelationship of parts by weight to parts is obtained which has goodfastness to light and water. by volume is as that of grammes to cubiccentimeters. Dyestuffs having similar properties are obtained if, Examl6 1 instead of the 24.0 parts of 2,4,5,6-tetracshloropyrimidine p theequivalent amount of 2,4,6-trichloro-5-bromopyrimidine,2,4,6-trichloropyrimidine, 2,4,6-tribromopyrimidine, 0 11 HOSS- H- -Q ccyanuric chloride, 2-amino-4,6-dichlorotriazine, Z-meth- I 1 A oxy4,6-dichlorotriazine, 2-(4-sulphophenylamino)-4,6- dichlorotriazine,fl-chloropropionyl chloride, fl-chlorocro- I tonic acid chloride,B-chloroacrylic acid chloride or vinyl s 03H OH Cl 1 carbonyl chlorideis used.

Similar dyestuffs are also obtained if, in the above 25.3 parts ofl-aminobenzene-2,S-disulphonic acid are example, instead of the1-am.inobenzene-2,5-disulphonic diazotised in the known manner andcoupled with 41.0 acid or the2-(3-aniinophenylureido)-5-hydroxynaphthaparts of2-(3-aminophenylureido)-5-hydroxynaphthalene-7-sulphonic acid, thecorresponding amount of one lene-7-sulphonic acid in the presence of 20parts of sodiof the diazo or coupling components given in the followingum bicarbonate. As soon as no more diazoniurn comtable is reacted withone of the acid halides or halogenpound can be traced, the dystuff isprecipitated wlth sodium azines listed in the previous paragraph.

Table 1 Dyc-stulf No. Diazo component Coupling component Shade 361cellulose HES l-aminobenzene-2,4-di-sulphonic acid2-(4-aminophenylureid0)-5-hydroxynaphthalene-7- Orange.

sulphonic acid. Z-aminonaphthalene-l,5-disulphonie acid. d0 Red-orange.do 2-(3-aminophenylureido)-5-hydroxynaphthalene-7- D0.

sulphonic acid. 2-aminonaphthalen04,6,8-trisulphoni0 acid do Do. do2-(3-aminophenylureido)8-hydroxynaphthalenefi- Red.

sulphonic acid. l-aminolocnzene-2,5-disu1phonie acid 0... Scarlet. do.1-(4-aminophenylureido)'8-hydroxynapthalene-4,6- Blueish red.

disulphonic acid. 2-aminonaphthalene-1,5disulphonic acid1-(3-aminopheny1ureido)-8-hydroxynaphthalcne-afi- Do.

(lisulphonie acid. do 1(3-aminopl1eny1ureido)-8-hydroxynaphthalcne 3,6-Bluish red.

disulphonic acid. .do 2-(3-an1inophenylureido)-6-hydroxynaphthalenc-B-Brown-orange.

Brown. Scarlet.

Blueish red.

disulphonic acid. 14 Adn 1-(3-aminopheuylureido)-8hydroxynaphthalenel,6-D0.

disulphonic acid. 15 do 1-(3-aminophenylureido)-5hydroxynaphthalene-7-Do.

sulphonic acid. lamin0-2-carb0xybenzene-E-sulphonic acid d0 Orange.l-amino-Z-carboxybenzene-i-sulphonic acid do Do. 1an1in0bcnzene-2,l-disulphonic acid 2(N-rnethylarninophenyl-ureido)-5-hydr0xynaph- D0.

thalene-7sulphonic acid. Q-aminonaphthalened,5-disulph0nic acid2'(3-N-methylamiuophenyl-ureido) -8-hydroxynapl1- thalene-G-sulphonieacid. Red.

EXAMPLE 2 chloride, filtered off, washed with dilute sodium chlorideSOsH 50.4 parts of 3-amino-3'-[2,5",6"-trichloropyrimdyl solution andagain dissolved at 65 in 500 parts of (4")-amino]-diphenylurea-4-sulphonic acid, in the form 1 l of the sodium salt, are pasted in400 parts of water, 6.9 parts of sodium nitrite are added and the wholeis added dropwise at 10-15 to 30 parts of concentrated hydrochloric acidand 200 parts of water. After stirring for 2 hours at 1015, the yellowdiazonium suspension is 12 acid and the 36.9 parts ofl-(2',5'-disulphophenyl)-3- methyl-S-pyrazolone, the correspondingamount of one of the diazo or coupling components given in the followingtable is used and the dyestuffs obtained are applied by the 5 dyeingprocess described.

Table 2 Dyestufi No. Diazo component Coupling component Shade iolncellulose Jrcs 1 3-amino-3-[2,5,6"-trichloropyrimidyl-(4)-amino]-l-hydroxynaphthalencl,G-disulphonic acid Scarlet.

dipheuyl urea--sulphonic acid.

2 do l-hydroxynaphthaleue-3,G-disulphonic acid Do.

2-hydroxyuaphthalone-c,7-disulphonic acid Red-orange.l-benzoglainino-8-hydroxynaphthalcne-S,G-disulphon- Blueish red.

acr l-pheupgureido-8-hydroxynaphthalone-4,6-disulpho11- Do.

10 acr 6.. ,do 1-(5 ,7 disulphonaphthyl-(2))-3-methyl-5-pyrazoloneYcllow.

7 3-ami11o-4 ic ri1nidy1-(4)-amin0]-dil-hydroxynaphthalone-4,(w-disulphouic acid Scarlet.

phenyl ureaulpnouic acid.

8 o 1-(2,5-disulph0phenyl)-3-mcthyl-5-pyrazolone 1- Yellow.

9 3-amino-3-[4"-methoxy-6chlorotriaziuyl-(2)-Z-hydroxynaphthalone-5,7-disulpl1onic acid Orange.

amino1-diphenyl uroa-4-sulphonic acid.

. .do l-phcn%ureido-8-hydroxynaphthalene-3,6-disulphon- Blucish red.

3-an1ino-3-(fl-chlorotonylamino)-diphenylureall-hydroxynaphthalene-4,7-disulphonic acid Scarlet.

sulphonic acid.

3-amino-3[-2",5",6-trichloropyrimidyl-(4)-methl-hydr0Xynaphthalenc-4,6-disulphouicacid D0.

ylamino]-diphonylurea--sulphonic acid.

3-amiuo3-[-B-sulphohydroxypropiouylamin0]-dipl1enl-hydroxynaphthalene-4,(S-disulphonicacid Do.

ylurca-4-sulphcnic acid.

do 1-hydroxynaphthalone-3,6-disulphouic acid Do.

poured into a solution of 36.9 parts ofl(2,5'-disu1phophenyl)-3-methyl-5-pyrazolone and parts of sodiumbicarbonate in 200 parts of water. As soon as no more diazonium groupscan be traced, the new yellow dyestufl. is precipated with sodiumchloride, filtered off, washed with dilute sodium chloride solution anddried in vacuo at 60-70. It is a yellow powder which dissolves in waterwith a yellow colour.

Cotton is impregnated with a solution which contains 20 parts of the newdyestufi, 20 parts of caustic soda lye of 36 Be. and parts of sodiumsulphate in 1000 parts of water, the goods are rolled up and stored for24 hours at 20-30". The lemon yellow dyeing is then rinsed and soaped atthe boil for 15 minutes. The dyeing has very good fastness to light andgood wet fastness properties and it can be discharged white both neutraland alkaline.

The 3-amino-3'-[2",5",6-trichl0ropyrimidyl (4")- arnino]-diphenylurea-4-sulphonic acid used in this eX- ample as diazo component isproduced by reacting 1,3-diaminobenzene-4-sulphonic acid with anequivalent 3-nitrophenyl isocyanate, reducing the nitro group to theamino group according to Bchamp and then condensing with theequimolecular amount of 2,4,5,6-tetrachloropyramidine.

Similar dyeings are obtained if, in the above example, instead of the50.4 parts of 3-amino-3-[2,5,6-trichloropyrimidyl-(4")-amino] diphenylurea-4-sulphonic EXAMPLE 3 3.9 parts of1-amino-3-[(2',5',6-trichloropyrimidyl- 50 (4))-methylamin0]benZene-6-sulphonic acid are dissolved in 300 parts of water to give aneutral reaction, first 6.9 parts of sodium nitrite and. then 25 partsof hydrochloric acid are added at 10-15 and the whole is stirred for 2hours at 10-15 The yellow diazonium suspension is then poured within 30minutes into a solution of 48.2 parts of 2-(4-sulphophenylureido)-5-hydroxynaphthalene-7-sulphonic acid and 40 parts of sodiumbicarbonate in 300 parts of water. After stirring for 3 hours, thecoupling is complete. The new dyestufi is precipiated with sodiumchloride, filtered off, washed with dilute sodium chloride solution anddried in vacuo at 6070. It is a red powder which dissolves in water withan orange-red colour.

Cotton is pad dyed with a solution of 20 parts of the new dyestutf, 20parts of sodium carbonate and 200 parts of urea in 1000 parts of Water,dried at 40, subjected for 4 minutes to a dry heat treatment at thenrinsed and soaped at the boil for 15 minutes. A pure orange-red dyeingis obtained which has good light and very good wet fastness properties.In addition, the dyeing can be discharged white both neutral andalkaline.

Dyestuffs having similar properties are obtained if, in the aboveexample, instead of the 36.9 parts of 1-amino-3-[(2',5',6'-trichloropyrimidyl-(4')) methyl amino1-benzene-6-sulphonicacid or the 48.2 parts of 2-(4-sulphophenylureido)hydroxynaphthalene-7-sulphonic acid,

the correspon ding amount of one of the diazo or coupling of sodiumchloride, filtered off, Washed With dilute sodium chloride solution anddried in vacuo.

It is a red powder which dissolves in water with a red-orange colour.

Table 3 Dyestufi No. Diazo component Coupling component Shade 191i;cellulose 1 res 1 1-amino3-[2,5,6-trichloropyrimidyl-(4)-methyl-2-(3-sulphophenylureldo) 8-liydroxynaphthalene-6 Scarlet.

amino1-benzenc-6-sulphonic acid. sulphonic acid. 2 do1-pl1e11ylureido-S-hydroxynaphthalone-3,6-disul- Red.

phonic acid. 3 do 2-(4-hydroxy-3-carhoxy-5-sulph0phenylureid0) -5-Orange.

hydroxynaphthalene-7-sulphonic acid. 4l-amino-3-[2,G-dichloropyrimidy1-(4)-amino]-bendo Do.

zene-ti-sulphonic acid. 51-amin0-3-[2',5,6-trichl0r0pyrimidyl-(4')-amino]-2-(4-sulphophenylureido)-5-hydroxynaphthalene-7- Do.

benzene-fi-sulphonic acid. phonic acid. 61-amino-3-[4,6-dichlorotriazinyl-(2)-amino]-benzenel-phenylureido-8-hydroxynaplithalenc4,6-rlisul-Blueish red.

6-sulphonic acid. phonic acid. 71-amino-3-[4-amino-G-chlorotriazinylamino-(2)]- do Do.

benzene-G-sulphonic acid. 8l-arnino-3-[4-ethoxy-fi-chlorotrlazinylamino-(2)]-l-phenylureido-lS-hydroxynaphthalone-3,6-disul- Do.

benzenefi-sulphonie acid. phonic acid. 91-amin0-3-[4-(3"-Su1phophenylamin0)-6-chlor0tri-2-(3-sulphophenylureido)-5-hydroxynapllthalene-7- Orange.

azinyl-(Z)-amino]-G-sulphonic acid. sulphonic acid. 10l-amino-B-(fi-chlorocrotonylamino)-benzene-6-suldo Do.

phonic acid. 11 1-argino-3- (q-chloropropionylamino) -benzene6-suld0 Do.

p onic ac 12 1-amino-3-[2,5,6-trich1oropyrimidyl-(4)-amino]-l-phenylureido-8-hydroxynaphthalene-4,(i-disul- Red.

benzene-[i-sulphonic acid. phonic acid. 131-amin0-3-[2,5',6-trichl0r0pyrimidyl-(4)-ethyl-2-(3-sulphophenylureido)-8-hydroxynapl1thalene6 Scarlet.

amino]-benzene-6-sulphonic acid. sulphonic acid. 14 ,do 2-(4-sulphophenylnreido)-5-hydroxynaphthalene-7- Orange.

sulphonic acid. 15 1-amin0'3-(fl-sulphohydroxypropionyl-amino)-2-(4-sulphophenylureido)-5-hydroxynaphthalene-7- Do.

benzene. sulphonic acid. 16 doLphenylureido-8-hydroxynaphthalenc-3,6-disul- Scarlet.

phonic acid.

38.7 parts EXAMPLE 4 of 3-amino-diphenylurea-4,4-disulph0nic acid, inthe form of the sodium salt, are dissolved in 300 parts of Water andfirst 6.9 parts of sodium nitrite and then parts of concentratedhydrochloric acid are added to the solution at 15.

After stirring for 2 hours at 1S- 20, the yellow diazonium suspension ispoured at 20-25 into a solution of 47.8 parts of2[(2,5',6-trichloropyrimidyl-(4) )-methyl-amino] 5 hydroXynaphthalene-7-sulphonic acid and parts of sodium carbonate in 400 parts of water. Assoon as no more diazonium groups can If cotton or staple fibre is dyedwith the new dyestutt by one of the methods described in Examples 1-3,then a strong red-orange dyeing having good wet and light fastnessproperties is obtained.

Dyestufls having similar properties are obtained if,

in the above example, instead of 38.7 parts of3-amino-diphenylurea-4,4-disulphonic acid or instead of the 47.8 partsof2-[(2,5',6'-trichloropyrimidyl-(4))-rnethyl-amino]-5-hydroxynaphthalene-7-sulphonicacid, one of the diazo or coupling components given in the followingtable be traced, the new dyestufi is precipltated by the addltion isused.

Table 4 Dyestuff No. Diazo component Coupling component Shade c1131cellulose res 1 3-arnino-diphenylurca-4,4disulphonic acid2-[(2,5',6-trichloropyrimidyl-(4'))-arnino]-8-hydroxy- Scarlet.

naphthalene-6- sulphonic acid.

2 do 1-[(4,6-dichlorotriazinyl-(2))-amino]-5-hydroxynaph- Red.

thalene-7-sulphonic acid.

3. d0 l-(fl-chlorocrotony]amino)-8-hydroxynaphthalcnc-3,6- Blucish red.

disulphonic acid.

4 3-amino-diphenylurca-4,3-disulphonic acid1-[(2,6-dichloropyrirnidyl-(4))-mcthyl-arnino]-S- Red.

hydroxynaphthalenc-3,6-disulphonic acid.

5 do l-(B-chloropropionylarnino)8-hydroxynaphthalenc-4, Do.

ddisulphonic acid.

6 do 2-[ (Y-am ino-6-chl0rotriazinyl- (2)) -mcthyl-amino1-8- Scarlet.

hydroxynaphthalene-G-sulphonic acid.

7 3-amino-4-hydroxy-3-carboxy-diphenylureai,5- .do Red.

disulphonic acid.

8 do 1-[(2,6-dichlorophyrimidylfl))-arnino]-8-hydroxy- Blueish red.

naphthalene-3,o-disulphonic acid.

9 dn l-acrgylamino-EhydroxynaphthalencAfi-disulphonic Do.

10 3-amino-diphenylurca-4A disulphonic acid2-[(2,5,6-trichloropyrimidyl-(4))-ethylamino]-S-hy- Scarlet.

droxynaphthalcnedsulphonic acid.

11. do l-[(4,6-dichlorotriazinyl-(2))ethylaminol-fi-hydroxy- Do.

naphthalene-7-sulphonic acid.

12 do 2-(B-sulphohydroxypropionylarnino)-5-hydroxy- Do.

naphthalene-7-sulphon1c acid.

is EXAMPLE 5 50 11 26.9 parts of1-amino-2-hydroxybenzene-3,S-disulphonic acid are diazotised in theusual way and coupled with 10 ame table.

Table Dyestufi Metal in Shade on N o. Diazo component Coupling componentcomplex cellulose linkage fibres 1l-amino-2-hydroxybenzene-3,5-disulphonic acid2-[3-(2,5",6-trichloropyrimidyl-(4")-arnin0) Cu Ruby red.

pheanylurcidol-S-hydroxynaphthalene-fi-sulphomc aci 2 do2-[3-(2,6"-diehloropyrimidyl-(4)-'imino]-phcn- Cu Do.

ylureido-fi-hydroxynaphthalene-7-sulphonic acid. 3l-amilno-2-hydroxy-G-nitro-naphthalcne-4-sulphonic "cdo Cr/Co. Black.

acir. 4 l-amino-5-[4,6-dichl0rotriazinyl-(2)-amino]-2-1-phenylureido-s-hydroxynaphthalone-4,6-disul- Cu Reddish blue.

hydroxybenzene-3-sulphonic acid. phonic acid. 5 d02-phenylureido-6hydr0xynaphthalenc-B-sulphonic Cr Black.

acid. 61-amin0-3-[4-(3-sulphophenylamino)-6-chl0rotril-phenylureid0-8-hydroxynaphthalene-3,6-disul-Cu Violet.

azinyl-(Q)-amino]-2-hydroxybenzeneS-sulphonic phonic acid. ac 7l-amino-2-hydroxybenzene-3,5-disulphonic acid1-[3-(B-chloroproplonylarnlno)-phenylureido]-8- Cu Do.

hydroxynaphthaleno-3,G-disulphonic acid. 8l-amino-2-hydroxybcnzenc-fi-mcthylsulphone1-[4-(fl-chlorocrotonylamin0)-pheuylureid0] 8- Cu a. D0.

l1ydroxynaphthalcne-4,6-disulphonic acid. 9. d01-[4-(3"-sulphophenylamino)-6-(chl0rotriazinyl- Cu Do.

(2)-an1ino)-phenylurcido]8-hydroxynaphthalene- 4,6-disulphonic acid. 10Z-arnlno-l-benzoic acid 2-[3-(2,5 -trichloropyrimidyl-(4)-amino)- CrBrown.

pl elnylureid0]-5-l1ydr0xynaphthalene-7-sulphonic aci 114-amlno3-carboxydiphcnylurea-4-sulphonlc acid "do Cr Do. 12 do1-[3-(2,5,6-trichl0r0pyrimidyl-(4)-amin0)- Cr Yellow.

phenyl1-3-methyl-S-pyrazolene. 136-(2,5,6-trichloropyrimidyl-(4)-amin0)-2-amin0-l-1-[3(4sulphophenylureido)-phenyl]-3-mcthyl-5- Co Brown-yellow.

hydroxybcnzenei-sulphonic acid. pyrazolone.

| I 01 Cl 69.8 parts of l-[3'-(2",5",6"-trichloropyrimidyl-(4")-amino-phenylureido] 8 hydroxynaphthalene-4,6-disulphonic acid in thepresence of parts of sodium bicarbonate. The dyestutf formed isprecipitated with sodium chloride, filtered off, washed with dilutesodium chloride solution, again dissolved in 500 parts of water (60warm) and parts of crystallised sodium acetate are added to thesolution. 25 parts of crystallised copper sulphate dissolved in 100parts of water are then poured in within 15 minutes and the whole isstirred for 30 minutes at The metallised monoazo dyestuff isprecipitated with sodium chloride, filtered off, Washed with dilutesodium chloride solution and dried in vacuo at 6070 It is a black powderwhich dissolves in water with a violet colour.

If cotton or staple fibre is dyed with the new dyestuff by one of themethods described in Examples l3, then a violet dyeing which has verygood wet and light fastness properties is obtained.

EXAMPLE 6 SOsI-I 81.9 parts of the aminomonoazo dyestutf of the formulain the form of the sodium salt, are dissolved in 500 parts of water at50 and 32.5 parts of 4-sulphophenylcarbamic acid phenolester are addedto the solution within 1 hour at this temperature. As soon as no morefree amino groups can be traced, the new dyestutf is precipitated withsodium chloride, filtered off, washed with dilute sodium chloridesolution and dried in vacuo at 6070. It is a dark red powder whichdissolves in water with a blueish-red colour.

If cotton or staple fibre is dyed with the new dyestuff by one of themethods described in Examples 1-3, then a brilliant, blueish red dyeinghaving good wet and light fastness properties is obtained.

A. L z

wherein E -N=NE is a moiety selected from the group consisting ofphenyl-azo-naphthyl, naphthyl-azo-naphthyl,1-pheny1-3-methyl-pyrazol-5-onyl-azo-pheny1,1-naphthyl-3-methyl-pyrazol-S-onyl-azo-phenyl and the aforesaid moietysubstituted with one of the substituents phenylureido, benzylamino,nitro, and methylsulfonyl,

D is a member selected from the group consisting of phenyl ando-hydroXy-carboxyphenyl,

R is a member selected from the group consisting of hydrogen and loweralkyl,

Z is a member selected from the group consisting of diand tri-halogenopyrimidyl-(4), mono-halogenas-triazinyl substituted with one of thesubstituents phenyl, alkoxy, alkylmercaptor, amino and phenylamino,dihalogeno-s-striazinyl, fi-halogeno-lower fatty acid, HO SO-CH -CH -Cand CHFCHCO wherein the halogen has an atomic weight of to 80,

one of n and n is zero and the other of n and n is 1,

one of Y and Y is -O and the other of Y and Y is a member selected fromthe group consisting of -O- and COO-,

each of Y and Y is linked to E and E respectively,

in ortho-position to the azo bridge,

Me is a metal selected from the group consisting of copper, chromium andcobalt,

q represents one of the whole numbers 3 to 5 inclusive and o-NHOsmH HOQSNmN 18 k represents one of the whole numbers 1 and 2 E being and Y beingH-Y when k is 1. 2. The reactive dyestuff of the formula NH-C O-NHQ-S 03151 OH 3. The reactive dyestuif of the formula slog]: NH-C O-NHOH 0 OHOH 4. The reactive dyestutf of the formula 01 CNH SO H OH NH-C 0-NH o 0S'aH 5. The reactive dyestuif of the formula 6. The reactive dyestufi ofthe formula.

S033: HOaS References Cited by the Examiner UNITED STATES PATENTS2,128,325 8/38 Rose et a1 260-151 2,891,941 6/59 Fasciati et al.260---153 2,945,021 7/60 Fasciati et al. 260-153 2,993,885 7/61 Fasciati260-153 3,004,022 10/61 Stephen 260--153 FOREIGN PATENTS 214,546 4/61Austria. 565,447 9/58 Belgium. 1,221,621 1/60 France. 1,225,281 2/60France. 1,110,460 10/55 France. 1,246,743 10/60 France.

87,960 4/58 Netherlands.

OTHER REFERENCES Capponi et al.: American Dyestuif Reporter July 10,

1961, pp. 23 to 32.

Wegmann: Textil Praxis, October 1958, pp. 1056- 1061.

CHARLES B. PARKER, Primary Examiner.

1. THE REACTIVE DYESTUFF OF THE FORMULA